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Nachbewilligung zur Dritten Phase des Projektes: Entwicklung eines zweistufigen biologischen Verfahrens zur Reinigung von Deponiesickerwasser und industriellen Abwässern mit komplexen Stoffgemischen

Zielsetzung und Anlass des Vorhabens: Ziel der letzten Projektphase war es, mit einer Langzeit-Praxiserprobung das zweistufige biologische Verfahren zur Deponiesickerwasserreinigung als Stand der Technik zu etablieren und zu bilanzieren. Nach der Inbetriebnahme des Technikums am Deponiestandort Schöneiche ging es in der zwölfmonatigen Laufzeit des Projektes AZ 14996/04 in den Langzeitversuchen um die Validierung der Laborergebnisse im technischen Maßstab, die verfahrenstechnische Optimierung der Anlage und um eine damit verbundene mögliche Kostenreduzierung des Systems. Darstellung der Arbeitsschritte und der angewandten Methoden: Nach dem ersten Technikums-Probebetrieb wurde eine Reihe von Optimierungsmaßnahmen durchgeführt: - der Umbau des Rohsickerwasserzulaufs, - die Verwendung von Soda statt Bicarbonat für die Ammoniumoxidation in Reaktor 2, - der Einsatz von Membrandosierpumpen mit integrierten Rückschlagventilen für die Zugabe von Soda und Essigsäure, - der Einbau von zusätzlichen Polyurethan-Festbetten zur Vergrößerung der Oberfläche für die Besiedlung mit Mikroorganismen, - die Einstellung des Sollwerts für Reaktor 4 auf einen pH-Wert von 6,5, - ein Update der SPS-Steuerung der Nanofiltration zur freien Programmierung der Spülzyklen, - der Einbau eines Absperrhahns vor den Nanofiltrations-Vorfilter - und die Trennung des Nanofiltrationsablaufs vom Reaktoren-Sammelablauf zur Behälterleerung. Es wurde sowohl Rohsickerwasser der MEAB-Deponie Schöneiche als auch Sickerwasserkonzentrat der Deponie Vorketzin behandelt. Fazit: Wegen der durchgeführten Optimierungsmaßnahmen ist es prinzipiell gelungen, das Schöneicher Rohsickerwasser gemäß Anhang 51 der Abwasserverordnung aufzureinigen. In Vorketzin wurde die organische Belastung über 70% und Stickstoff über 80% reduziert. Nach Rückgang der Calciumfracht sollte es zukünftig möglich sein, mit der Zweistufen-Biologie das Sickerwasserkonzentrat ausreichend zu reinigen, da organische Belastung und Stickstoffgehalt geringer als im Schöneicher Rohsickerwasser sind. Um das Verfahren als Stand der Technik, vor allem für die Behandlung von Sickerwasserkonzentraten, zu etablieren, müssten die Laborvorgaben mit den Erfahrungen des Technikumsbetriebs kombiniert und in einer weiteren Versuchsreihe unter optimierten Bedingungen verifiziert werden.

International Collaboration in Chemistry: First Principles Multi-Lattice Kinetic Monte Carlo Simulations of NOx Storage Reduction Catalysts

The broad objective of the research is to gain a fundamental understanding of the surface reaction chemistry of exhaust catalysts operating under cycling conditions. Using an integrated theoretical approach we specifically target NOx abatement, with particular emphasis on the appearance and destruction of surface oxide phases as the reactor conditions cycle from oxidative to reductive during the operation of the NOx Storage Reduction (NSR) catalyst system. Methodologically this requires material-specific, quantitative and explicitly time-dependent simulation tools that can follow the evolution of the system over the macroscopic time-scales of NSR cycles, while simultaneously accounting for the atomic-scale site heterogeneity and spatial distributions at the evolving surface. To meet these challenging demands we will develop a novel multi-scale methodology relying on a multi-lattice first-principles kinetic Monte Carlo (kMC) approach. As representative example the simulations will be carried out on a PdO(101)/Pd(100) surface oxide model, but care will be taken to ensure a generalization of the multi-lattice first-principles kMC approach to other systems in which phase transformations may occur and result in a change in the surface lattice structure depending upon environmental variables.

Release of hexavalent chromium from ore processing residues and the potential of biochar for chromium immobilization in polluted soils

Chromium (Cr) is introduced into the environment by several anthropogenic activities. A striking ex-ample is the area around Kanpur in the Indian state of Uttar Pradesh, where large amounts of Cr-containing wastes have been recently illegally deposited. Hexavalent Cr, a highly toxic and mobile contaminant, is present in significant amounts in these wastes, severely affecting the quality of sur-roundings soils, sediments, and ground waters. The first major goal of this study is to clarify the solid phase speciation of Cr in these wastes and to examine its leaching behavior. X-ray diffraction and synchrotron-based X-ray absorption spectroscopy techniques will be employed for quantitative solid phase speciation of Cr. Its leaching behavior will be studied in column experiments performed at un-saturated moisture conditions with flow interruptions simulating monsoon rain events. Combined with geochemical modeling, the results will allow the evaluation of the leaching potential and release kinetics of Cr from the waste materials. The second major goal is to investigate the spatial distribution, speciation, and solubility of Cr in the rooting zone of chromate-contaminated soils surrounding the landfills, and to study the suitability of biochar as novel soil amendment for mitigating the deleterious effects of chromate pollution. Detailed field samplings and laboratory soil incubation studies will be carried out with two agricultural soils and biochar from the Kanpur region.

Forschergruppe (FOR) 986: Structural Change in Agriculture, How should Model Linkages be designed to analyze the Effects of Global Agricultural Trade Liberalization at the Farm Level?

In the last decades agricultural policy has gained increasingly in complexity. Nowadays it influences the food and agricultural sector from the global market down to the farm level. Widespread research questions, like the impact of the WTO negotiations on the farm structure, most often require comprehensive modeling frameworks. Thus, different types of models are utilized according to their comparative advantages and combined in a strategically useful way to more accurately represent micro and macro aspects of the food and agricultural sector. Consequently, in recent years we have seen an increase in the development and application of model linkages. Given this background, the overall objective of this subproject is a systematic sensitivity analysis of model linkages that gradually involves more and more characteristics of the linkage and the corresponding transfer of results between models. In addition, the project aims to answer the following specific question: How does structural change at the farm level influence aggregate supply and technical progress? Under which conditions is it possible to derive macro-relationships from micro-relationships? How does the aggregation level influence the model results and how can possible problems be overcome? This procedure is used to quantify the effects and to derive conditions for optimal interaction of the connected models. The analysis is based on the general equilibrium model GTAP (Global Trade Analysis Project) and the farm group model FARMIS (Farm Modelling Information System) which are employed in conjunction to analyze the effects of WTO negotiations on the farm level.

Biogenic soil structures: feedbacks between bioactivity and spatial heterogeneity of water storage and fluxes from plot to hillslope scale

Soil structure determines a large part of the spatial heterogeneity in water storage and fluxes from the plot to the hillslope scale. In recent decades important progress in hydrological research has been achieved by including soil structure in hydrological models. One of the main problems herein remains the difficulty of measuring soil structure and quantifying its influence on hydrological processes. As soil structure is very often of biogenic origin (macropores), the main objective of this project is to use the influence of bioactivity and resulting soil structures to describe and support modelling of hydrological processes at different scales. Therefore, local scale bioactivity will be linked to local infiltration patterns under varying catchment conditions. At hillslope scale, the spatial distribution of bioactivity patterns will be linked to connectivity of subsurface structures to explain subsurface stormflow generation. Then we will apply species distribution modelling of key organisms in order to extrapolate the gained knowledge to the catchment scale. As on one hand, bioactivity influences the hydrological processes, but on the other hand the species distribution also depends on soil moisture contents, including the feedbacks between bioactivity and soil hydrology is pivotal for getting reliable predictions of catchment scale hydrological behavior under land use change and climate change.

Transport of EINP through soil affected by the dynamics of infiltration flux and particle properties

In this project we experimentally explore the transport of engineered inorganic nanoparticles (EINP) through soils. This is done for original EINPs and some pre-aged form. Transport of NPs in soil is expected to be different from that of reactive solutes, in that hydrodynamic drag, inertial and shear forces as well as the affinity to water-gas interfaces are expected to be more relevant. Hence, the mobility of EINPs in soil is highly sensitive to the morphology of the porous structure and the dynamics of water saturation.This project provides the pore network structure for natural soils using X-ray micro-tomography to allow for an up-scaling of pore-scale interactions explored by project partners to the scale of soil horizons. The pore structure is represented by a network model suitable for pore scale simulations including the dynamics of water-gas interfaces.Pore network simulations will be compared to column experiments for conservative tracers as well as for unaltered and pre-aged EINPs (obtained from INTERFACE). This includes steady state flow scenarios for saturated (ponding) and unsaturated conditions as well as for transient flow to explore the impact of moving water-gas interfaces. The final goal is to arrive at a consistent interpretation of experimental findings and numerical simulations to develop a module for modelling EINP transfer through soil as a function of particle properties, soil structural characteristics and external forcing in terms of flux boundary conditions.

Schwerpunktprogramm (SPP) 1315: Biogeochemische Grenzflächen in Böden; Biogeochemical Interfaces in Soil, Quantification of active interfaces with respect to dissolved chemicals in unsaturated structured soil

During the first project period we developed a general approach to quantify soil pore structure based on X-ray micro-tomography Vogel et al. (2010) which is applicable at various scales to cover soil pores larger that 0.05 mm in a representative way. Based on this method we generated equivalent network models to numerically simulate flow and transport of dissolved chemicals. The existing network model was extended to handle reactive transport and infiltration processes which are especially critical for matter flux in soil. The results were compared to experimental findings. The original research question 'what does a particle see on its way through soil' could be answered quantitatively for various boundary conditions including steady state flux and infiltration. However, we identified various critical aspects of the proposed modeling concept which will be in the focus of the second period. This includes 1) the spatial arrangement of interfaces having different quality which is crucial for chemical interactions and pore scale water dynamics, 2) the realistic multiphase dynamics at the pore scale which need to reflect the dynamic pressure and movement of trapped non-wetting phase and 3) the parametrization of structural complexity which need to be developed beyond the measurement of continuous Minkowski functions to allow the development of quantitative relations between structure and function. These aspects will be explored in a joint experiments in cooperation with partners within the SPP.

Redox processes along gradients

The relevance of biogeochemical gradients for turnover of organic matter and contaminants is yet poorly understood. This study aims at the identification and quantification of the interaction of different redox processes along gradients. The interaction of iron-, and sulfate reduction and methanogenesis will be studied in controlled batch and column experiments. Factors constraining the accessibility and the energy yield from the use of these electron acceptors will be evaluated, such as passivation of iron oxides, re-oxidation of hydrogen sulfide on iron oxides. The impact of these constraints on the competitiveness of the particular process will then be described. Special focus will be put on the evolution of methanogenic conditions in systems formerly characterized by iron and sulfate reducing condition. As methanogenic conditions mostly evolve from micro-niches, methods to study the existence, evolution and stability of such micro-niches will be established. To this end, a combination of Gibbs free energy calculations, isotope fractionation and tracer measurements, and mass balances of metabolic intermediates (small pool sizes) and end products (large pool sizes) will be used. Measurements of these parameters on different scales using microelectrodes (mm scale), micro sampling devices for solutes and gases (cm scale) and mass flow balancing (column/reactor scale) will be compared to characterize unit volumes for organic matter degradation pathways and electron flow. Of particular interest will be the impact of redox active humic substances on the competitiveness of involved terminal electron accepting processes, either acting as electron shuttles or directly providing electron accepting capacity. This will be studied using fluorescence spectroscopy and parallel factor analysis (PARAFAC) of the gained spectra. We expect that the results will provide a basis for improving reactive transport models of anaerobic processes in aquifers and sediments.

Calcium cycling in the soil-fig-bat compartment of a neotropical rain forest on spatially heterogeneous substrate

Calcium supply in tropical soils is variable and frequently low. In spite of the heterogeneous Ca supply, some plant species, such as figs, maintain high Ca concentrations in their tissues. Figs are keystone species with more than proportional importance for the functioning of a tropical rain forest. High Ca concentrations in fig fruits may render them particularly attractive for frugivorous vertebrates. We propose to study the whole Ca cycling from soil through a selected fig species, Ficus insipida Willd. and frugivorous bats, their main dispersers, back to soil. The study will be conducted in Panama on sites differing in soil Ca status to assess the importance of soil Ca availability for fig fruit content and bat reproduction. We will quantify aboveground Ca fluxes for 16 trees along a gradient of Ca availability in soil. We will determine (1) Ca concentrations in soils, figs and leaves, (2) nutritional quality of fig and other bat-dispersed fruits and their importance for Ca balance in relation to reproduction of fruit-eating bats, (3) Ca fluxes with litterfall, throughfall, stemflow, bat pellets and faeces, (4) the importance of the contribution of bats to the Ca cycle of individual fig trees, and (5) the effect of fig trees on soil Ca concentrations.

Non-destructive characterization and monitoring of root structure and function at the rhizotron and field scale using spectral electrical impedance tomography (ImpTom)

This subproject aims at the development of spectral electrical impedance tomography (EIT) as a non-destructive tool for the imaging, characterization and monitoring of root structure and function in the subsoil at the field scale. The approach takes advantage of the capacitive properties of the soil-root interface associated with induced electrical polarization processes at the root membrane. These give rise to a characteristic electrical signature (impedance spectrum), which is measurable in an imaging framework using EIT. In the first project phase, the methodology is developed by means of controlled rhizotron experiments in the laboratory. The goal is to establish quantitative relationships between characteristics of the measured impedance spectra and parameters describing root system morphology, root growth and activity in dependence on root type, soil type and structure (with/without biopores), as well as ambient conditions. Parallel to this work, sophisticated EIT inversion algorithms, which take the natural characteristics of root system architecture into account when solving the inherent inverse problem, will be developed and tested in numerical experiments. Thus the project will provide an understanding of electrical impedance spectra in terms of root structure and function, as well as specifically adapted EIT inversion algorithms for the imaging and monitoring of root dynamics. The method will be applied at the field scale (central field trial in Klein-Altendorf), where non-destructive tools for the imaging and monitoring of subsoil root dynamics are strongly desired, but at present still lacking.

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